Aluminum based metallic glass powder for efficient degradation of azo dye and other toxic organic chemicals

ABSTRACT

The present invention provides amorphous bi-functional catalytic aluminum metallic glass particles having an aluminum metallic glass core and 2 or more transition metals disposed on the surface of the aluminum metallic glass core to form amorphous bi-functional aluminum metallic glass particles with catalytic activity.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority based on U.S. Provisional ApplicationNo. 62/281,941, filed Jan. 22, 2016. The contents of which isincorporated by reference in its entirety.

TECHNICAL FIELD OF THE INVENTION

The present invention relates generally to methods and compositions usedfor the removal of organic dye and organic pollutants from a solution,and more specifically to the degradation of AZO dyes and organicpollutants.

STATEMENT OF FEDERALLY FUNDED RESEARCH

None.

INCORPORATION-BY-REFERENCE OF MATERIALS FILED ON COMPACT DISC

None.

BACKGROUND OF THE INVENTION

Without limiting the scope of the invention, its background is describedin connection with the degradation of AZO dyes and organic pollutants.AZO dyes, generated from industrial waste, create an alarming threat astoxic water pollutant and carcinogen. A very recent study reported thatAZO dyes decrease the permeability of blood-brain barrier, which mayresult in chronic neurological disorder in the human body. Transitionmetals (Fe, Ni) and noble metals (Pt, Pd) have been used to degrade anddetoxify different organic water pollutants, including AZO dye. Noblemetals typically show high catalytic activity. However, high cost,scarcity, and susceptibility to catalyst poisoning limit theirapplication as water purifier. Thus, late transition metals like Fe, Ni,and Fe-Ni bi-metallic catalyst are attractive owing to their low cost,excellent catalytic performance, and easy availability in differentforms. However, poor durability and high reactivity in aqueous mediumrestrict their potential use as a water purifier. In addition, thesemetals in elemental form exhibit wide range of toxicity in human bodyincluding cancer formation.

U.S. Patent No. 9,149,673, entitled, “Removal of organic dyes andorganic pollutants by titanium peroxide gel,” discloses a one stepprocess of removal of chromophore/dye/organic pollutant from a solutioncomprising a polymer free titanium oxide gel i.e. high zeta potential isdisclosed. The concentration of the chromophores is removed up to95-100%.

China Patent Application No. 1415565, entitled, “Method for treatingwaste water of azo dye,” discloses a process for treating the sewagecontaining azo dye includes such steps as regulating pH value to lessthan 2.5, adding iron powder, stirring for decoloring, and radiating byultraviolet light for optical degradation. Its advantages are high speedand effect, and no secondary pollution.

China Patent Application No. 104174380, entitled, “Greenenvironment-friendly degradable adsorption material for azo dyeindustrial wastewater,” discloses a green environment-friendlydegradable adsorption material for azo dye industrial wastewater ischaracterized by comprising the following substances in parts by weight:10-32 parts of acrylic high-molecular water-absorption material, 3-9parts of phosphoric acid, 5-14 parts of concentrated hydrochloric acid,14-26 parts of ethanol, 5-16 parts of ammonia water, 3-6 parts of gallicacid, 2-6 parts of citric acid, 1-6 parts of diatomite, 3-8 parts ofperforated expanded perlite, and 4-11 parts of a phosphite anti-oxidant.The beneficial effects comprise that the green environment-friendlydegradable adsorption material is high in adsorption property, iscapable of adsorbing azo dye molecules in azo dye wastewater into a tinynetwork to reach the effect of efficiently absorbing azo dye moleculesin wastewater, and is good in processing effect; and also dye wastessubjected to adsorption can be used as a pigment of plastic and buildingmaterials.

China Patent Application No. 103585998, entitled, “Material for treatingazo dye industrial wastewater,” discloses a material for treating azodye industrial wastewater, which is characterized by comprising thefollowing components in parts by weight: 10-32 parts of acrylic acidhigh-polymer water-absorbing resin, 10-25 parts of bagasse, 1-2 parts ofnano calcium sulfate, 2-7 parts of titanate coupling agent, 0.1-0.3 partof nano silver, 1-2 parts of maleic anhydride graft polypropylene, 2-3parts of polyethylene terephthalate, 10-16 parts of cement ash watersolution, 9-15 parts of ferric oxide, 1-3 parts of high-densitypolyethylene (HDPE), 3-4 parts of toughener EOC and 1-3 parts of stearicacid. The material has high absorptivity, can adsorb azo dye moleculesin azo dye wastewater into small networks, achieves the effect ofefficiently absorbing azo dye molecules in wastewater, and has favorabletreatment effect. The dye waste after adsorption can be used as apigment for plastics and building materials.

SUMMARY OF THE INVENTION

The present invention provides amorphous bi-functional catalyticaluminum metallic glass particles comprising an aluminum metallic glasscore and 2 or more transition metals disposed on the surface of thealuminum metallic glass core to form amorphous bi-functional aluminummetallic glass particles with catalytic activity. The amorphousbi-functional aluminum metallic glass particle surface has a lowconcentration of the 2 or more transition metals. The amorphousbi-functional aluminum metallic glass particles react to degrade azocompounds and/or reacts with azo groups. The 2 or more transition metalsmay be Y, Ni and Fe. The 2 or more transition metals may be Scandium,Titanium, Vanadium, Chromium, Manganese, Iron, Cobalt, Nickel, Copper,Zinc, Yttrium, Zirconium, Niobium, Molybdenum, Technetium, Ruthenium,Rhodium, Palladium, Silver, Cadmium, Hafnium, Tantalum, Tungsten,Rhenium, Osmium, Iridium, Platinum, Gold, Mercury, Rutherfordium,Dubnium, Seaborgium, Bohrium, Hassium, Meitnerium, Ununnilium,Unununium, and Ununbium. The aluminum may be at least 80% of thecomposition. The aluminum may be at least 80%, Y comprises at least 5%,Ni comprises at least 4% and Fe comprises at least 1% of thecomposition. The aluminum may be 77-87%, Y comprises 5-11%, Ni comprises4-10% and Fe comprises 1-5% of the composition. The aluminum may beabout 82%, Y comprises about 8%, Ni comprises about 7% and Fe comprisesabout 3% of the composition. The amorphous bi-functional aluminummetallic glass particles may be Al₈₂Y₈Ni₇Fe₃. The composition of claim1, wherein the amorphous bi-functional aluminum metallic glass particlesmay have a diameter of greater than 500 nm. The amorphous bi-functionalaluminum metallic glass particles have a diameter of 0.5-40 μm. The azocompounds may be Orange II (C₁₆H₁₁N₂NaO₄S), Chrysoidine (C₁₂H₁₃CIN₄),Tropaeolin O (C₁₂H₉N₂NaO₅S), Acid Orange, and Acid Red.

The present invention provides a method of making an amorphousbi-functional metallic glass powder for catalytic activity comprisingthe steps of: heating an metal composition to a molten metal, whereinthe metal composition comprises aluminum, yttrium, nickel, and iron;contacting the molten metal with a high pressure gas jet to atomize themolten metal to form amorphous bi-functional aluminum metallic glassparticles with catalytic activity; and collecting the amorphousbi-functional aluminum metallic glass particles. The amorphousbi-functional aluminum metallic glass particle surface has a lowconcentration of the 2 or more transition metals. The amorphousbi-functional aluminum metallic glass particles react to degrade azocompounds and/or reacts with azo groups. The 2 or more transition metalsmay be Y, Ni and Fe. The 2 or more transition metals may be Scandium,Titanium, Vanadium, Chromium, Manganese, Iron, Cobalt, Nickel, Copper,Zinc, Yttrium, Zirconium, Niobium, Molybdenum, Technetium, Ruthenium,Rhodium, Palladium, Silver, Cadmium, Hafnium, Tantalum, Tungsten,Rhenium, Osmium, Iridium, Platinum, Gold, Mercury, Rutherfordium,Dubnium, Seaborgium, Bohrium, Hassium, Meitnerium, Ununnilium,Unununium, and Ununbium. The aluminum may be at least 80% of thecomposition. The aluminum may be at least 80%, Y comprises at least 5%,Ni comprises at least 4% and Fe comprises at least 1% of thecomposition. The aluminum may be 77-87%, Y comprises 5-11%, Ni comprises4-10% and Fe comprises 1-5% of the composition. The aluminum may beabout 82%, Y comprises about 8%, Ni comprises about 7% and Fe comprisesabout 3% of the composition. The amorphous bi-functional aluminummetallic glass particles may be Al₈₂Y₈Ni₇Fe₃. The composition of claim1, wherein the amorphous bi-functional aluminum metallic glass particlesmay have a diameter of greater than 500 nm. The amorphous bi-functionalaluminum metallic glass particles have a diameter of 0.5-40 μm. The azocompounds may be Orange II (C₁₆H₁₁N₂NaO₄S), Chrysoidine (C₁₂H₁₃CIN₄),Tropaeolin O (C₁₂H₉N₂NaO₅S), Acid Orange, and Acid Red.

The present invention provides an amorphous bi-functional aluminummetallic glass catalyst comprising: an aluminum metallic glass core; and2 or more transition metals disposed on the surface of the aluminummetallic glass core to form amorphous bi-functional aluminum metallicglass particles with catalytic activity. The amorphous bi-functionalaluminum metallic glass particle surface has a low concentration of the2 or more transition metals. The amorphous bi-functional aluminummetallic glass particles react to degrade azo compounds and/or reactswith azo groups. The 2 or more transition metals may be Y, Ni and Fe.The 2 or more transition metals may be Scandium, Titanium, Vanadium,Chromium, Manganese, Iron, Cobalt, Nickel, Copper, Zinc, Yttrium,Zirconium, Niobium, Molybdenum, Technetium, Ruthenium, Rhodium,Palladium, Silver, Cadmium, Hafnium, Tantalum, Tungsten, Rhenium,Osmium, Iridium, Platinum, Gold, Mercury, Rutherfordium, Dubnium,Seaborgium, Bohrium, Hassium, Meitnerium, Ununnilium, Unununium, andUnunbium. The aluminum may be at least 80% of the composition. Thealuminum may be at least 80%, Y comprises at least 5%, Ni comprises atleast 4% and Fe comprises at least 1% of the composition. The aluminummay be 77-87%, Y comprises 5-11%, Ni comprises 4-10% and Fe comprises1-5% of the composition. The aluminum may be about 82%, Y comprisesabout 8%, Ni comprises about 7% and Fe comprises about 3% of thecomposition. The amorphous bi-functional aluminum metallic glassparticles may be Al₈₂Y₈Ni₇Fe₃. The composition of claim 1, wherein theamorphous bi-functional aluminum metallic glass particles may have adiameter of greater than 500 nm. The amorphous bi-functional aluminummetallic glass particles have a diameter of 0.5-40 μm. The azo compoundsmay be Orange II (C₁₆H₁₁N₂NaO₄S), Chrysoidine (C₁₂H₁₃CIN₄), Tropaeolin O(C₁₂H₉N₂NaO₅S), Acid Orange, and Acid Red.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the features and advantages of thepresent invention, reference is now made to the detailed description ofthe invention along with the accompanying figures and in which:

FIG. 1a shows an X-ray diffraction analysis showing the amorphous natureof the Aluminum metallic glass (AlMG) particles.

FIG. 1b shows a differential scanning calorimetry (DSC) whichillustrates the sharp glass transition (T_(g)) and crystallizationtemperature (T_(x)).

FIG. 1c shows a scanning electron micrograph (SEM) image of AlMGparticles which demonstrates the particles size in the range between 0.5μm to 20 μm.

FIG. 1d shows the particle size analysis distribution of the particles,where significant percentages of the particles are in the size range of0.5 μm to 5 μm.

FIG. 2a is an image showing the color change of AZO dye (left picture)from deep blue to transparent (right picture) after reaction withAl-BMG. The middle picture shows the AZO dye after reaction withstate-of-the-art zero valent iron powder and the brownish solutionclearly demonstrates that Fe produces reaction by-product and unable todissociate the dye completely.

FIG. 2b shows a UV-Visible absorption spectrum demonstrates that thesolution became completely transparent after reacting with AlMGparticles.

FIG. 2c shows a normalized intensity versus time plot illustrates thatamorphous AlMG particles are faster in degrading AZO dye compared totheir crystalline counterpart as well as current state-of-the-art zerovalent iron powder.

FIGS. 3a and 3b show the state-of-the-art zero valent iron powder beforeand after the reaction, to AZO dye, respectively.

FIGS. 3c and 3d show AlMG particles before and after the reaction,respectively.

FIGS. 4a and 4b show scanning electron micrograph (SEM) of AlMGparticles showing the surface properties before reaction.

FIGS. 4c and 4d show scanning electron micrograph (SEM) of AlMGparticles showing the surface properties after reaction.

FIG. 5a shows a Raman spectrum of pure AZO dye before reaction and afterreaction with AlMG particles showing complete dissociation of AZO dye.

FIG. 5b shows an infrared spectrum demonstrating the complete breakingof —C—H—and —C—N—bonds of AZO dye.

FIG. 5c shows an equation illustrating the catalyzing reaction ofmetallic glass for AZO dye degradation.

FIGS. 6a and 6b show X-ray photoelectron spectrum of (FIG. 6a ) Fe2p_(3/2) and (FIG. 6b ) Ni 2p_(3/2) obtained from AlMG particles beforeand after reaction, respectively.

FIG. 7a shows an X-ray photoelectron spectrum of AlMG particle surfaceshowing the Aluminum 2p1/2 peaks before reaction and FIG. 7b afterreaction to the AZO dye.

FIG. 7c shows an X-ray photoelectron spectrum of AlMG particle surfaceshowing the Yttrium 3d peaks before the reaction and FIG. 7d afterreaction to the AZO dye.

FIG. 8a shows an illustration of the bi-functional mechanism of AZO dyedegradation using metallic glass particles. FIG. 8b illustrates thechemical reaction occurring as a catalytic degradation of the AZO dye.

DETAILED DESCRIPTION OF THE INVENTION

While the making and using of various embodiments of the presentinvention are discussed in detail below, it should be appreciated thatthe present invention provides many applicable inventive concepts thatcan be embodied in a wide variety of specific contexts. The specificembodiments discussed herein are merely illustrative of specific ways tomake and use the invention and do not delimit the scope of theinvention.

To facilitate the understanding of this invention, a number of terms aredefined below. Terms defined herein have meanings as commonly understoodby a person of ordinary skill in the areas relevant to the presentinvention. Terms such as “a”, “an” and “the” are not intended to referto only a singular entity, but include the general class of which aspecific example may be used for illustration. The terminology herein isused to describe specific embodiments of the invention, but their usagedoes not delimit the invention, except as outlined in the claims.

In aqueous medium, zero-valent transition metal ions (ZVTMI) (e.g. Fe)produce toxic reaction by-products such as rust (Fe₂O₃·nH₂O). Recently,Fe-based and Mg-based metallic glasses have been found to be veryeffective in degradation of organic chemicals including AZO dye.Metallic glasses (MG) are amorphous multi-component alloys that haveattracted lot of interest due to their high catalytic activity, chemicalinertness, and durability. The higher catalytic activity of thezero-valent amorphous alloys compared to their corresponding crystallinecounterpart is attributed to their lower activation energy for electrontransfer and uniform dispersion of the catalytically active componentsin a chemically homogeneous environment. In addition, large number oflow-coordination atoms and defect sites promote catalytic reactions inamorphous systems. Uniform and random distribution of atoms in metallicglasses allows continuous control of their electronic and catalyticproperties along with homogeneous surface reactivity. Recently, it hasbeen found that addition of Ni to Fe facilitates electron transport andenhances bimetallic catalytic activity.

The present invention provides a small percentage of transition metal(Fe—Ni) constituents in a mostly aluminium alloy having extraordinarilyhigh catalytic activity, with no toxic by-product and no change insurface characteristics. The amorphous nature of the alloy renders itinert and durable during the reaction, while promoting high surfacecatalytic activity at the same time. The advantages of this type ofconfiguration include (i) a small percentage of transition metals arecatalytically effective without any toxic by-products; (ii) aluminium isitself non-catalytic, however, its high electrical conductivity promotesfast charge transfer for the catalytic reaction; and (iii) light-weightAl-alloy particles are easily dispersed in any solution, thus,accelerating the homogeneous redox reactions. In addition, the effect ofstructure (amorphous versus crystalline) as well as the ionization stateof the surface catalyst species on the reaction rate is demonstrated.Although there are several reports on AZO dye dissociation usingmetallic glasses, however, lack of dye degradation mechanism limitsunderstanding in this field including further development. By combiningRaman, Infrared (IR) spectroscopy, and X-ray photoelectron spectroscopy(XPS), the dye dissociation mechanism is shown and demonstrate thebi-functional (simultaneous change in ionization states of Ni and Fe)catalytic activities of metal at this amorphous alloy surface.

Differential Scanning Calorimetry (DSC). The glass transitiontemperature (T_(g)) and the crystallization temperature (T_(x)) for theAlMG powder were measured using a differential scanning calorimeter(DSC) (NETZSCH STA 449 F3). About 5 mg of the sample was placed in analumina crucible and was heated from 473K to 873K in inert (Ar)atmosphere. The rate of heating was kept at 20 K/min during thiscalorimetric measurement.

X-ray Diffraction (XRD). The phase formed in as-received AlMG particleswere identified using an X-ray diffractometer (Rigaku Ultima) with thesamples exposed to Cu Kα radiation of wavelength of 1.54 Å. For X-raydiffraction measurement, all the samples were placed on the clay, whichwas mounted on a glass slide.

Scanning Electron Microscopy (SEM). The microstructure of the AlMGparticles was observed using scanning electron microscope (FEI ESEM).All micrographs were captured at a voltage of 15KV with a workingdistance of ˜5 mm. The powdery samples were dispersed in a liquid mediumfollowed by drop casting onto a Si substrate in order to image using theSEM.

UV-Visible Spectroscopy. Commercially available AZO Dye(C₃₂H₂₀N₆Na₄O₁₄S₄) ) was purchased from Sigma-Aldrich and 0.015 molardye solution was prepared after mixing the equivalent amount of powderwith deionized water.

The AlMG particles were dispersed in dye solution followed by sonicationfor 5-7 minutes. The absorption spectra of the solution were measuredusing UV Visible spectroscopy. The instrument was calibrated and themeasurement baseline was corrected using deionized water before eachmeasurement.

Raman and IR Spectroscopy. After the reaction, all the metal particleswere extracted from solution and dried overnight under ambientatmospheric condition for the further characterization by Raman and IRspectroscopy.

Raman Spectroscopy. Raman spectroscopy was carried out for all the AlMGsamples at room temperature from the frequency 0 to 4500. The Ramanspectrometer (Enwave Optronics Inc., Pro Raman-L) used for theseexperiments is inbuilt with green Ar laser with wavelength 532 nm.

Infrared Spectroscopy. The Infra-red (IR) spectroscopy was obtainedusing an IR spectrophotometer (PerkinElmer Spectrum FT-IRSpectrophotometer) equipped with both transmission and ATR modes. The IRSpectrometer was used for data collection over a wave number range of370-7800 cm⁻¹ using a fast recovery deuterated triglycine sulfatedetector with KBr splitting. All the data collected using IRspectrophotometer was quantitatively analyzed using Spectrum Onesoftware.

X-ray photoelectron spectroscopy (XPS). X-ray photoelectron spectroscopy(XPS) was carried out using a PHI 5000 Versaprobe x-ray photoelectronspectrometer. The XPS instrument was equipped with a high-flux x-raysource, which provides a highly focused monochromatic x-ray beam thatcan be used to scan the sample surface. Similarly, the spectroscopicdata was recorded in an XPS system which incorporates a high-resolution180° spherical capacitor energy analyzer, which provides full-featuredXPS analysis. A 100-5 kV differentially pumped argon ion gun was usedwith a regulated leak valve for specimen cleaning by sputtering withmono-layer atomic resolution.

FIG. 1a shows an X-ray diffraction analysis showing the amorphous natureof the Aluminium metallic glass (AlMG) particles. FIGURE 1b shows adifferential scanning calorimetry (DSC) illustrates the sharp glasstransition (T_(g)) and crystallization temperature (T_(x)). Aluminium(Al) metallic glass (AlMG) powder of composition Al (82%) Y (8%) Ni (7%)Fe (3%) was synthesized by arc-melting the constituent elements followedby the gas-atomization process. The structure of synthesized metallicglass powder was investigated by X-ray diffraction (XRD) anddifferential scanning calorimetry (DSC) as shown in FIGURES 1a and brespectively. A broad hump without any crystalline peaks depicts thefully amorphous nature of the particles (FIG. 1a ). FIG. 1b shows theDSC curve with a glass transition temperature (T_(g)) of 232° C.,primary crystallization temperature (T_(x1)) of 304° C., and secondarycrystallization temperature (T_(x2)) of 384° C. A wide super-cooledregion of ΔT (=T_(x1)−T_(g)) ˜72°C. indicates good thermal stability ofthis powder. FIG. 1c shows a scanning electron micrograph (SEM) image ofAlMG particles demonstrates the particles size in the range between 0.5μm to 20 μm. Scanning electron micro-graph (SEM) is shown in the FIG. 1c, which demonstrate the smooth and spherical nature of the particles.FIG. 1d shows the particle size analysis distribution of the particles,where a significant percentage of the particles are in the size range of0.5 μm to 5 μm. FIG. 1d shows the histogram of particle sizes, asignificant percentage of particles being in the size range of 0.5-5 μm.

FIG. 2a is an image showing the color change of AZO dye (left picture)from deep blue to transparent (right picture) after reaction withAl-BMG. The middle picture shows the AZO dye after reaction withstate-of-the-art zero valent iron powder and the brownish solutionclearly demonstrates that Fe produces reaction by-product and unable todissociate the dye completely. AZO dye degradation tests were performedin a UV-VISIBLE spectrometer at room temperature. The absorption peaksof the dye solution were characterized before and after reaction withAlMG. Sonication was carried out during each experiment in order todisperse the particles in solution to initiate a homogeneous reactionwith the dye molecules. As shown in FIG. 2a , the dark blue AZO dyesolution became colorless after the reaction. UV-VIS data was collectedas a function of time, where the absorption peak intensity diminished asthe dye molecules continually degraded and the solution turned clear.FIG. 2b shows a UV-Visible absorption spectrum demonstrates that thesolution became completely transparent after reacting with AlMGparticles. AlMG powder degrades the AZO dye in less than 40 minutes,whereas state-of-the-art zero valent iron particles in the same sizerange took more than 60 minutes for the reaction. Even after 60 minutesthe Fe powder was unable to degrade the dye completely and there werereaction by-products as shown in FIG. 2a (the middle picture shows thatthe solution is reddish brown and is not clear). After the reaction,both the AlMG and the pure Fe powder were extracted and dried overnightin ambient condition. There was no color change in AlMG particles afterthe reaction, whereas a clear color change was observed for thecrystalline Fe particles from gray to yellowish brown. FIG. 2c shows anormalized intensity versus time plot illustrates that amorphous AlMGparticles are faster in degrading AZO dye compared to their crystallinecounterpart as well as current state-of-the-art zero valent iron powder.To obtain the rate of degradation reaction we normalized the intensitywith the initial AZO dye absorption intensity. The slopes of the curvesdemonstrate the reaction rate, which is faster for AlMG compared to zerovalent iron particles of the same size range. The amorphous AlMGparticles were crystallized by going above the crystallizationtemperature in DSC and performed the same reaction with AZO dye solutionfollowed by UV-VIS absorption tests. The normalized intensity plot shows(FIG. 2c ) a flat line for crystalline AlMG samples depicting no changein the color of AZO dye. Thus, the surface catalytic activity is highfor the amorphous particles but not for the corresponding crystallizedones. This is likely due to the formation of complex intermetallicphases with no catalytic activity.

FIGS. 3a and 3b show the state-of-the-art zero valent iron powder beforeand after the reaction, to AZO dye, respectively. FIGS. 3c and 3d showAlMG particles before and after the reaction, respectively. The changein color of Fe particles is attributed to the formation of harmfulby-products of iron oxides/hydroxides as reported earlier. In contrast,there was no color change for AlMG particles, confirming the excellentdurability of the amorphous particles. Furthermore, we investigated themorphological stability of AlMG particles before and after the reactionand no changes were observed on the particle surface after 40 minutereaction as shown in FIGS. 4a-4d . FIGS. 4a and 4b show scanningelectron micrograph (SEM) of AlMG particles showing the surfaceproperties before reaction. FIGS. 4c and 4d show scanning electronmicrograph (SEM) of AlMG particles showing the surface properties afterreaction.

FIG. 5a shows a Raman spectrum of pure AZO dye before reaction and afterreaction with AlMG particles showing complete dissociation of AZO dye.FIG. 5b shows an infrared spectrum demonstrating the complete breakingof —C—H—and —C—N—bonds of AZO dye. FIG. 5c shows an equationillustrating the catalyzing reaction of metallic glass for AZO dyedegradation. FIGS. 5a and 5b show the comparative plots of Raman andinfra-red (IR) spectroscopy respectively, of the pure AZO dye and theparticles after the reactions. In Raman and IR, it was observed that thecharacteristic —C—H—, —C—N—, and —N═N—bond peaks of AZO dye are absentafter the reaction. The absence of these bonds justifies thatdegradation of AZO dye takes place via surface activated redox reactionas shown in FIG. 5 c.

FIGS. 6a and 6b show X-ray photoelectron spectrum of (a) Fe 2p_(3/2) and(b) Ni 2p_(3/2) obtained from AlMG particles before and after reaction,respectively. X-ray photoelectron spectroscopy (XPS) was performed tofurther elucidate the mechanism of surface redox reaction as shown inFIGS. 6a and 6 b.

FIG. 7a shows an X-ray photoelectron spectrum of AlMG particle surfaceshowing the Aluminum 2p1/2 peaks before reaction and FIG. 7b afterreaction to the AZO dye. FIG. 7c shows an X-ray photoelectron spectrumof AlMG particle surface showing the

Yttrium 3d peaks before the reaction and FIG. 7d after reaction to theAZO dye. The surface composition of the AlMG particles were analyzedbefore and after reaction and no change in surface composition werefound for each of the constituents. FIG. 7 shows the comparative X-rayphotoelectron spectroscopy (XPS) peak positions of Al 2p_(1/2) and Y3_(3/2) respectively, and no significant changes are found for Al and Ypeaks before and after the reaction. Al is non-catalytic and does notundergo any change in its ionization state. However, the high percentageof aluminum in the alloy likely promotes rapid charge transfer due toits high electrical conductivity. Yttrium (Y) is a rare-earth transitionmetal, which promotes glass formation in this alloy system, but does notseem to participate in the catalytic redox reaction. Te XPS peakpositions and shape of Fe 2p_(3/2) for the catalyst-particles before andafter reaction were noted as shown in FIG. 4a . The position of Fe2p_(3/2) peak was at ˜706 eV before reaction and shifted towards higherbinding energy of 711.8 eV after reacting with AZO dye molecules. Thispeak shift is a clear representation of the change towards higherionization state of Fe during the redox reaction. Similarly, peak shifttowards higher binding energy for Ni justifies the change of itsionization state after reaction as shown in the FIG. 4 b.

FIG. 8a shows the schematic of the mechanism of the dissociation of AZODye. FIG. 8b shows the chemical reaction occurring as a catalyticdegradation of the AZO dye. After fitting and the de-convolution ofpeaks, both Fe and Ni atoms were found on the surface of the metallicglass particles move towards higher binding energy state during thecatalytic redox reaction. This simultaneous change in ionization stateof the transition metal constituents likely contributes to the highcatalytic activity of AlMG. In the process, the transition metals donateelectrons to the redox reaction for AZO dye dissociation as illustratedin FIGS. 8a and 8b . Bimetallic transition metal catalysts boost thekinetics of redox reactions by enhancing the charge transfer twofoldover any single-metal catalyst. At the same time, the amorphousstructure promotes high durability without the formation of any toxicby-products.

The bi-functional catalysis mechanism of amorphous metals in degradingAZO Dye is successfully demonstrated. A small amount of transitionmetals together with highly conducting aluminum in an amorphousconfiguration promotes catalytically active surface-mediated redoxprocess without any harmful byproduct formation. The amorphous powder isfound to be superior compared to state-of-the-art zero valent ironpowder with particles in the same size range. The simultaneous change inionization state of the transition metal constituents contributes to thehigh catalytic activity of the metallic glass and opens up a newparadigm for designing new (bi-functional) catalysts. In addition, thisbi-functional catalysis mechanism of amorphous metals can be furtherexplored in efficient degradation of variety of other organic waterpollutants, e.g. Acid orange IV, Orange I, Acid orange II, Acid red 3B,Acid orange GG, and several others.

Aluminum based metallic glass (AlMG) powder of composition Al₈₂Y₈Ni₇Fe₃was found to be an efficient catalyst for the degradation of toxicorganic chemicals, including, AZO dye (C₃₂H₂₀N₆Na₄O₁₄S₄), which is acarcinogen and toxic water pollutant. AlMG powder was synthesized by gasatomization and the particle size was found to be in the range of 10-40μm. The reaction of AlMG with AZO dye solution results in completedissociation in less than 40 minutes. In addition, no harmful toxicbyproducts are generated from the reaction, making it an environmentallyfriendly process. Thus, this novel material provides rapid degradationof organic environmental pollutants.

Variation in the composition may affect the following properties of thecatalyst powder: amorphous structure; catalytic charge transfer; AZO dyedegradation rate; bi-to-tri metallic catalytic system; corrosionresistance; mechanical properties; dissociation of many other types oforganic water pollutants; and reuse the particles multiple times andreduce waste.

The present invention provides a more efficient technology that theexisting technology; degrades the organic chemicals faster than existingmethods; degrades organic chemicals at room temperature; doesn't requireany stringent conditions for the reaction; is nonhazardous; doesn'tproduce any harmful byproducts after the reaction; exhibits higherdurability; and reduces the cost for waste management and handling.

It is contemplated that any embodiment discussed in this specificationcan be implemented with respect to any method, kit, reagent, orcomposition of the invention, and vice versa. Furthermore, compositionsof the invention can be used to achieve methods of the invention.

It will be understood that particular embodiments described herein areshown by way of illustration and not as limitations of the invention.The principal features of this invention can be employed in variousembodiments without departing from the scope of the invention. Thoseskilled in the art will recognize, or be able to ascertain using no morethan routine experimentation, numerous equivalents to the specificprocedures described herein. Such equivalents are considered to bewithin the scope of this invention and are covered by the claims.

All publications and patent applications mentioned in the specificationare indicative of the level of skill of those skilled in the art towhich this invention pertains. All publications and patent applicationsare herein incorporated by reference to the same extent as if eachindividual publication or patent application was specifically andindividually indicated to be incorporated by reference.

The use of the word “a” or “an” when used in conjunction with the term“comprising” in the claims and/or the specification may mean “one,” butit is also consistent with the meaning of “one or more,” “at least one,”and “one or more than one.” The use of the term “or” in the claims isused to mean “and/or” unless explicitly indicated to refer toalternatives only or the alternatives are mutually exclusive, althoughthe disclosure supports a definition that refers to only alternativesand “and/or.” Throughout this application, the term “about” is used toindicate that a value includes the inherent variation of error for thedevice, the method being employed to determine the value, or thevariation that exists among the study subjects.

As used in this specification and claim(s), the words “comprising” (andany form of comprising, such as “comprise” and “comprises”), “having”(and any form of having, such as “have” and “has”), “including” (and anyform of including, such as “includes” and “include”) or “containing”(and any form of containing, such as “contains” and “contain”) areinclusive or open-ended and do not exclude additional, unrecitedelements or method steps.

The term “or combinations thereof” as used herein refers to allpermutations and combinations of the listed items preceding the term.For example, “A, B, C, or combinations thereof” is intended to includeat least one of: A, B, C, AB, AC, BC, or ABC, and if order is importantin a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB.Continuing with this example, expressly included are combinations thatcontain repeats of one or more item or term, such as BB, AAA, AB, BBC,AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan willunderstand that typically there is no limit on the number of items orterms in any combination, unless otherwise apparent from the context.

All of the compositions and/or methods disclosed and claimed herein canbe made and executed without undue experimentation in light of thepresent disclosure. While the compositions and methods of this inventionhave been described in terms of preferred embodiments, it will beapparent to those of skill in the art that variations may be applied tothe compositions and/or methods and in the steps or in the sequence ofsteps of the method described herein without departing from the concept,spirit and scope of the invention. All such similar substitutes andmodifications apparent to those skilled in the art are deemed to bewithin the spirit, scope and concept of the invention as defined by theappended claims.

REFERENCES:

J.-Q. Wang, Y.-H. Liu, M.-W. Chen, G.-Q. Xie, D. V. Louzguine-Luzgin, A.Inoue, et al., “Rapid Degradation of Azo Dye by Fe-Based Metallic GlassPowder,” Advanced Functional Materials, vol. 22, pp. 2567-2570, 2012.

J.-Q. Wang, Y.-H. Liu, M.-W. Chen, D. V. Louzguine-Luzgin, A. Inoue, andJ. H. Perepezko, “Excellent capability in degrading azo dyes byMgZn-based metallic glass powders,” Sci. Rep., vol. 2, 05/23/online2012.

Y. F. Zhao, J. J. Si, J. G. Song, Q. Yang, and X. D. Hui, “Synthesis ofMg—Zn—Ca metallic glasses by gas-atomization and their excellentcapability in degrading azo dyes,” Materials Science and Engineering: B,vol. 181, pp. 46-55, 2// 2014.

What is claimed is:
 1. Amorphous bi-functional catalytic aluminummetallic glass particles comprising: an aluminum metallic glass core;and 2 or more transition metals disposed on the surface of the aluminummetallic glass core to form amorphous bi-functional aluminum metallicglass particles with catalytic activity.
 2. The composition of claim 1,wherein an amorphous bi-functional aluminum metallic glass particlesurface has a low concentration of the 2 or more transition metals. 3.The composition of claim 1, wherein the amorphous bi-functional aluminummetallic glass particles reacts to degrade azo compounds.
 4. Thecomposition of claim 1, wherein the 2 or more transition metals are Niand Fe.
 5. The composition of claim 1, wherein the 2 or more transitionmetals are Y, Ni and Fe.
 6. The composition of claim 1, wherein the 2 ormore transition metals are selected from Scandium, Titanium, Vanadium,Chromium, Manganese, Iron, Cobalt, Nickel, Copper, Zinc, Yttrium,Zirconium, Niobium, Molybdenum, Technetium, Ruthenium, Rhodium,Palladium, Silver, Cadmium, Hafnium, Tantalum, Tungsten, Rhenium,Osmium, Iridium, Platinum, Gold, Mercury, Rutherfordium, Dubnium,Seaborgium, Bohrium, Hassium, Meitnerium, Ununnilium, Unununium, andUnunbium.
 7. The composition of claim 1, wherein the aluminum comprisesat least 80% of the composition.
 8. The composition of claim 1, whereinthe aluminum comprises at least 80%, Y comprises at least 5%, Nicomprises at least 4% and Fe comprises at least 1% of the composition.9. The composition of claim 1, wherein the aluminum comprises 77-87%, Ycomprises 5-11%, Ni comprises 4-10% and Fe comprises 1-5% of thecomposition.
 10. The composition of claim 1, wherein the aluminumcomprises about 82%, Y comprises about 8%, Ni comprises about 7% and Fecomprises about 3% of the composition.
 11. The composition of claim 1,wherein the amorphous bi-functional aluminum metallic glass particlescomprises Al₈₂Y₈Ni₇Fe₃.
 12. The composition of claim 1, wherein theamorphous bi-functional aluminum metallic glass particles have adiameter of greater than 500 nm.
 13. The composition of claim 1, whereinthe amorphous bi-functional aluminum metallic glass particles have adiameter of 0.5-40 μm.
 14. The composition of claim 3, wherein the azocompounds are selected from Orange II (C₁₆H₁₁N₂NaO₄S), Chrysoidine(C₁₂H₁₃CIN₄), Tropaeolin O (C₁₂H₉N₂NaO₅S), Acid Orange, and Acid Red.15. A method of making an amorphous bi-functional metallic glass powderfor catalytic activity comprising the steps of: heating a metalcomposition to a molten metal, wherein the metal composition comprisesaluminum, yttrium, nickel, and iron; contacting the molten metal with ahigh pressure gas jet to atomize the molten metal to form amorphousbi-functional aluminum metallic glass particles with catalytic activity;and collecting the amorphous bi-functional aluminum metallic glassparticles.
 16. The method of claim 15, wherein the amorphousbi-functional aluminum metallic glass particles have a diameter of0.5-40 μm.
 17. The method of claim 15, wherein the amorphousbi-functional aluminum metallic glass particles comprises Al₈₂Y₈Ni₇Fe₃.18. The method of claim 15, wherein the aluminum comprises at least 80%of the composition.
 19. The method of claim 15, wherein the aluminumcomprises at least 80%, Y comprises at least 5%, Ni comprises at least4% and Fe comprises at least 1% of the composition.
 20. The method ofclaim 15, wherein the aluminum comprises 77-87%, Y comprises 5-11%, Nicomprises 4-10% and Fe comprises 1-5% of the composition.
 21. The methodof claim 15, wherein the aluminum comprises about 82%, Y comprises about8%, Ni comprises about 7% and Fe comprises about 3% of the composition.22. The method of claim 15, wherein the amorphous bi-functional aluminummetallic glass particles comprises Al₈₂Y₈Ni₇Fe₃.
 23. Amorphousbi-functional aluminum metallic glass catalyst comprising: an aluminummetallic glass core; and 2 or more transition metals disposed on thesurface of the aluminum metallic glass core to form amorphousbi-functional aluminum metallic glass particles with catalytic activity.24. The catalyst of claim 23, wherein the amorphous bi-functionalaluminum metallic glass particles comprises Al₈₂Y₈Ni₇Fe₃.
 25. Thecatalyst of claim 23, wherein the aluminum comprises at least 80%, Ycomprises at least 5%, Ni comprises at least 4% and Fe comprises atleast 1% of the composition.